JPH08239329A - Production of alpha-olefin oligomer - Google Patents

Abstract

PURPOSE: To obtain an α-olefin oligomer in high yield and selectivity by realizing selective trimerization of the α-olefin through specific contact with a specific chromium catalyst. CONSTITUTION: Using, as a chromium catalyst, a catalyst system comprising (a) a chromium compound such as chromium (III) 2-ethylhexanoate; (b) at least one selected from amines, amides and imides such as 2,5-dimethylpyrrol, (c) an alkylaluminum such as triethylaluminum, and (d) a halogen-containing compound such as tetrachloroethane, the catalyst components containing at least (c) and (d) selected from (b) through (d) are heated over 100 deg.C in a solvent such as heptane, then the rest of the catalyst components and the α-olefin such as ethylene are reacted at 0-250 deg.C. The molar ratio of the catalyst components is a:b:c:d=1:(0.1-10):(l-100):(0.1-: 20).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an α-olefin low polymer, and more particularly, to a high yield of an α-olefin low polymer mainly composed of ethylene and 1-hexene. The present invention relates to a method for producing an industrially advantageous α-olefin low polymer which can be produced with a high selectivity.

[0002]

2. Description of the Related Art Conventionally, as a method for low polymerization of α-olefin such as ethylene, there has been known a method of using a chromium-based catalyst comprising a combination of a specific chromium compound and a specific organoaluminum compound. For example, Japanese Patent Publication No.
No. 8707 describes a method for obtaining 1-hexene from ethylene with a catalyst system consisting of a Group VIA transition metal compound containing chromium and polyhydrocarbyl aluminum oxide.

Further, in JP-A-3-128904, α-olefin is trimerized by using a catalyst obtained by previously reacting a chromium-containing compound having a chromium-pyrrolyl bond with a metal alkyl or Lewis acid. How to do is described.

[0004]

By the way, in the industrial production method of the α-olefin low polymer, it is extremely important to increase the selectivity of the catalytic reaction as much as possible from the viewpoint of improving the utilization efficiency of the raw materials. . The present invention has been made in view of the above circumstances, and an object thereof is a method for producing an α-olefin polymer having a specific chromium-based catalyst, in which 1-hexene is the main component of ethylene. An object of the present invention is to provide an industrially advantageous method for producing an α-olefin low polymer, which is capable of producing an α-olefin low polymer in high yield and high selectivity.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have found that a compound (b) containing at least one selected from the group consisting of a chromium compound (a), an amine, an amide and an imide, an alkylaluminum compound (c) and a halogen-containing compound. In the catalyst system comprising the combination of (d), if the specific components among these catalyst components are preheated and then subjected to the preparation of the catalyst components,
It was found that the selectivity of the catalytic reaction is improved.

The present invention has been achieved on the basis of the above findings, and the gist thereof is α-using a chromium-based catalyst.
In the method for producing an olefin low polymer, as a chromium-based catalyst, at least one compound (b) selected from the group consisting of a chromium compound (a), an amine, an amide and an imide, an alkylaluminum compound (c) and a halogen-containing compound are contained. A catalyst system comprising a combination of compounds (d) was used, and a catalyst component containing at least (c) and (d) among the catalyst components (b) to (d) was heated to 100 ° C. or higher in a reaction solvent. Then, a method for producing an α-olefin low polymer, which comprises contacting the remaining catalyst component and α-olefin.

Hereinafter, the present invention will be described in detail. In the present invention, as the chromium-based catalyst, at least one compound (b) selected from the group consisting of chromium compound (a), amine, amide and imide, alkylaluminum compound (c) and halogen-containing compound (d). A catalyst system consisting of a combination of

The chromium compound used in the present invention is represented by the general formula CrXn. However, in the general formula, X represents an arbitrary organic group or inorganic group or a negative atom, n represents an integer of 1 to 6, and when n is 2 or more, X may be the same or different from each other. Good. The valence of chromium is 0 to 6, and n in the above formula is preferably 2 or more.

Examples of the organic group include various groups having usually 1 to 30 carbon atoms. Specific examples thereof include a hydrocarbon group, a carbonyl group, an alkoxy group, a carboxyl group, a β-diketonate group, a β-ketocarboxyl group, a β-ketoester group and an amide group. Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an aralkyl group, a cyclopentadienyl group and the like. Examples of the inorganic group include a chromium salt-forming group such as a nitrate group and a sulfate group, and examples of the negative atom include oxygen and halogen.

The preferred chromium compound is an alkoxy salt of chromium, a carboxyl salt, a β-diketonate salt, a salt of β-ketoester with an anion, or a chromium halide, and specifically, chromium (IV) tert-butoxide. , Chromium (III) acetylacetonate, chromium (III)
Trifluoroacetylacetonate, chromium (III) Hexafluoroacetylacetonate, chromium (III) (2
2,6,6-tetramethyl-3,5-heptanedionate), Cr (PhCOCHCOPh) ₃ (provided that P is
h represents a phenyl group. ), Chromium (II) acetate, chromium (III) acetate, chromium (III) 2-ethylhexanoate, chromium (III) benzoate, chromium (III) naphthenate, Cr (CH ₃ COCHCOOCH ₃ ) ₃ , chromium (III) chloride , Chromium chloride, chromium bromide, chromium bromide, chromium iodide, chromium iodide, chromium fluoride, chromium fluoride and the like.

Further, a complex composed of the above-mentioned chromium compound and an electron donor can also be preferably used. The electron donor is selected from compounds containing nitrogen, oxygen, phosphorus or sulfur.

Examples of the nitrogen-containing compound include nitriles, amines, amides, and the like. Specifically, acetonitrile, pyridine, dimethylpyridine, dimethylformamide, N-methylformamide, aniline, nitrobenzene, tetramethylethylenediamine, diethylamine,
Examples include isopropylamine, hexamethyldisilazane, and pyrrolidone.

Examples of oxygen-containing compounds include esters, ethers, ketones, alcohols, aldehydes,
Specific examples include ethyl acetate, methyl acetate, tetrahydrofuran, dioxane, diethyl ether, dimethoxyethane, diglyme, triglyme, acetone, methyl ethyl ketone, methanol, ethanol, acetaldehyde and the like.

Examples of phosphorus-containing compounds include hexamethylphosphamide, hexamethylphosphorus triamide, triethylphosphite, tributylphosphine oxide and triethylphosphine. On the other hand, examples of the sulfur-containing compound include carbon disulfide, dimethyl sulfoxide, tetramethylene sulfone, thiophene and dimethyl sulfide.

Therefore, as an example of a complex composed of a chromium compound and an electron donor, a chromium halide ether complex,
Ester complex, ketone complex, aldehyde complex, alcohol complex, amine complex, nitrile complex, phosphine complex,
Examples thereof include thioether complexes. Specifically, Cr
Cl ₃ / 3THF, CrCl ₃ / 3dioxane, C
_{rCl 3 · (CH 3 CO 2} n-C 4 H 9), CrCl 3
_{· (CH 3 CO 2 C 2} H 5), CrCl 3 · 3 (i-C
₃ H ₇ OH), CrCl ₃ · 3 [CH ₃ (CH ₂ ) ₃ C
H (C ₂ H ₅ ) CH ₂ OH], CrCl ₃ / 3pyri
_{dine, CrCl 3 · 2 (i} -C 3 H 7 NH 2),
[CrCl ₃ · 3CH ₃ CN] · CH ₃ CN, CrCl
_{3 · 3PPh 3, CrCl 2 ·} 2THF, CrCl 2 ·
2pyridine, CrCl ₂ · 2 [(C ₂ H ₅ ) ₂ N
H], CrCl ₂ · 2CH ₃ CN, CrCl ₂ · 2 [P
(CH ₃ ) ₂ Ph] and the like.

As the chromium compound, a compound soluble in a hydrocarbon solvent is preferable, and a β-diketonate salt of chromium,
Carboxylates, salts with anions of β-ketoesters, β
-Ketocarboxylic acid salts, amide complexes, carbonyl complexes, carbene complexes, various cyclopentadienyl complexes, alkyl complexes, phenyl complexes and the like. Examples of various carbonyl complexes of chromium, carbene complexes, cyclopentadienyl complexes, alkyl complexes, and phenyl complexes include Cr (CO) ₆ , (C ₆ H ₆ ) Cr (CO) ₃ ,
(CO) ₅ Cr (= CCH ₃ (OCH ₃ )), (CO)
₅ Cr (= CC ₆ H ₅ (OCH ₃ )), CpCrCl ₂
(Where Cp represents a cyclopentadienyl group), (
Cp * CrClCH ₃ ) ₂ (where Cp * represents a pentamethylcyclopentadienyl group), (CH ₃ ) ₂ CrC
1 and the like are exemplified.

The chromium compound can be used by supporting it on a carrier such as an inorganic oxide, but it is preferable to use it in combination with other catalyst components without supporting it on the carrier. That is, in the present invention, the chromium-based catalyst is used in a specific contact mode described later, but according to such a mode, high catalytic activity can be obtained without supporting the chromium compound on the carrier. When the chromium compound is used without being loaded on the carrier, the loading on the carrier which involves complicated operations can be omitted, and the total amount of the catalyst used (the total amount of the carrier and the catalyst component) is increased by the use of the carrier. It is possible to avoid the problem.

The amine used in the present invention is a primary or secondary amine.
It is a class amine. Examples of primary amines include ethylamine, isopropylamine, cyclohexylamine, benzylamine, aniline, naphthylamine, and the like.
As the secondary amine, diethylamine, diisopropylamine, dicyclohexylamine, dibenzylamine,
Bis (trimethylsilyl) amine, morpholine, imidazole, indoline, indole, pyrrole, 2,5-
Dimethylpyrrole, 3,4-dimethylpyrrole, 3,4
-Dichloropyrrole, 2,3,4,5-tetrachloropyrrole, 2-acylpyrrole, pyrazole, pyrrolidine and the like are exemplified.

Examples of the amide used in the present invention include metal amides derived from primary or secondary amines, such as the above primary or secondary amines and Group IA.
Mention may be made of amides obtained by reaction with metals selected from groups IIA, IIIB and IVB. Specific examples of such metal amides include lithium amide, sodium ethylamide, calcium diethylamide, lithium diisopropylamide, potassium benzylamide, sodium bis (trimethylsilyl) amide, lithium indolide, sodium pyrrolide, lithium pyrrolide and potassium. Examples thereof include pyrrolide, potassium pyrrolidide, aluminum diethylpyrrolide, ethylaluminum dipyrrolide and aluminum tripyrolide.

In the present invention, the above-mentioned secondary amine,
Metal amides derived from secondary amines or mixtures thereof are preferably used. Particularly, as the secondary amine, pyrrole, 2,5-dimethylpyrrole, 3,4-dimethylpyrrole, 3,4-dichloropyrrole, 2,3,3.
4,5-tetrachloropyrrole, 2-acylpyrrole,
As the metal amide derived from the secondary amine, aluminum pyrrolide, ethylaluminum dipyrrolide, aluminum tripyrolide, sodium pyrrolide, lithium pyrrolide and potassium pyrrolide are preferable. Among the pyrrole derivatives, those having a hydrocarbon group on the pyrrole ring are particularly preferable.

Examples of the amide or imide compound other than the above used in the present invention include compounds represented by the following general formulas (1) to (3).

[0022]

Embedded image

In the general formula (1), M ¹ is a hydrogen atom or a metal element selected from the groups IA, IIA and IIIB of the periodic table, and R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. , An alkenyl group, an aralkyl group, an aryl group which may have a substituent, or an aryl group which may contain a hetero element, and R ² represents a hydrogen atom or a carbon number of 1 to 1.
30 alkyl group, alkenyl group, aralkyl group, aryl group optionally having substituent (s), aryl group optionally containing hetero element, or acyl group C (═O) R
³ (R ³ is the same definition as R ^1, R ¹ and may be different) represents, R ¹ and R ² may form a ring.

In the general formula (2), M ² and M ³ are hydrogen atoms or metal elements selected from the groups IA, IIA and IIIB of the periodic table, and R ⁴ and R ⁵ are hydrogen atoms and carbon numbers. 1
To 30 represents an alkyl group, an alkenyl group, an aralkyl group, an aryl group which may have a substituent, or an aryl group which may contain a hetero element, and R ⁴ and R ⁵ form a ring. Or, A represents an alkylene group which may contain an unsaturated bond.

In the general formula (3), M ⁴ is a hydrogen atom or a metal element selected from groups IA, IIA and IIIB of the periodic table, and R ⁶ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms. , An alkenyl group, an aralkyl group, an aryl group which may have a substituent, or an aryl group which may contain a hetero element, and R ⁷ represents a hydrogen atom or a carbon number of 1 to 1.
30 alkyl group, alkenyl group, aralkyl group, aryl group which may have a substituent, aryl group which may contain a hetero element, or SO ₂ R ⁸ group (R ⁸ is the same definition as R ⁶ And may be different from R ⁶ ), and R ⁶ and R ⁷ may form a ring.

Examples of the amides represented by the general formula (1) or (2) include acetamide, N-methylhexanamide, succinamide, maleamide, N-methylbenzamide, imidazole-2-carboxamide, Examples include di-2-thenoylamine, β-lactam, δ-lactam, ε-caprolactam, and salts thereof with a metal of Group IA, IIA or IIIB of the periodic table.
Examples of the imides include 1,2-cyclohexanedicarboximide, succinimide, phthalimide, maleimide, 2,4,6-piperidinetrione, perhydroazecin-2,10-dione, and those of the periodic table. Mention may be made of salts with metals of group IA, IIA or IIIB.

Examples of the sulfonamides and sulfonimides represented by the general formula (3) are benzenesulfonamide, N-methylmethanesulfonamide, N-
Methyltrifluoromethylsulfonamide and salts of these with metals of Group IA, IIA or IIIB of the Periodic Table. Among these amide or imide compounds, the compound represented by the general formula (1) is preferable, and particularly,
An imide compound in which R ² in the general formula (1) represents an acyl group C (═O) R ³ and R ¹ and R ² form a ring is preferable.

In the present invention, an alkylaluminum compound represented by the following general formula (4) is preferably used as the alkylaluminum compound.

[0029]

Embedded image R ¹ _m Al (OR ² ) _n H _p X _q (4)

In the general formula (4), R ¹ and R ² are hydrocarbon groups having a carbon number of usually 1 to 15, preferably 1 to 8 and may be the same or different from each other. Represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p
Represents a number of 0 ≦ p <3, q represents a number of 0 ≦ q <3, and represents a number of m + n + p + q = 3.

Examples of the above-mentioned alkylaluminum compound include trialkylaluminum compounds represented by the following general formula (5), halogenated alkylaluminum compounds represented by the general formula (6), and alkoxy groups represented by the general formula (7). Examples thereof include an aluminum compound and an alkylaluminum hydride compound represented by the general formula (8). The meanings of R ¹ , X and R ² in each formula are the same as above.

[0032]

Embedded image R ¹ ₃ Al (5) R ¹ _m AlX _3-m (m is 1.5 ≦ m <3) (6) R ¹ _m Al (OR ² ) _3-m ( m is 0 <m <3, preferably 1.5 ≦ m <3) (7) R ¹ _m AlH _3-m (8) (m is 0 <m <3, preferably 1. 5 ≦ m <3)

Specific examples of the above alkylaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, diethylaluminum ethoxide, diethylaluminum hydride and the like. Among these, trialkylaluminums are particularly preferable in that the amount of polymer by-products is small. The alkylaluminum compound may be a mixture of two or more kinds.

In the present invention, the halogen-containing compounds include IIIA, IIIB, IVA and IV of the periodic table.
A halogen-containing compound containing an element selected from the group consisting of B, VA and VB is preferably used. And, as the halogen, chlorine or bromine is preferable.

Specific examples of the above halogen-containing compound include scandium chloride, yttrium chloride, lanthanum chloride, titanium tetrachloride, zirconium tetrachloride, hafnium tetrachloride, boron trichloride, aluminum chloride, diethylaluminum chloride, ethylaluminum sesquichloride. , Gallium chloride, carbon tetrachloride, chloroform, methylene chloride, dichloroethane, trichloroethane, tetrachloroethane, hexachlorobenzene, 1,3,5-trichlorobenzene, hexachlorocyclohexane, trityl chloride, tetrachlorosilane, trimethylchlorosilane,
Germanium tetrachloride, tin tetrachloride, tributyltin chloride, phosphorus trichloride, antimony trichloride, trityl hexachloroantimonate, antimony pentachloride, bismuth trichloride, boron tribromide, aluminum tribromide, carbon tetrabromide, bromoform, bromo Examples thereof include benzene, iodomethane, silicon tetrabromide, hexafluorobenzene, aluminum fluoride and the like.

Among the above halogen-containing compounds, those having a large number of halogen atoms are preferable, and compounds soluble in the reaction solvent are preferable. Examples of particularly preferable halogen-containing compounds include carbon tetrachloride, chloroform, dichloroethane, tetrachloroethane, titanium tetrachloride, germanium tetrachloride, tin tetrachloride and the like. The halogen-containing compound may be used as a mixture of two or more kinds.

In the present invention, 1 selected from the group of the above-mentioned chromium compound (a), amine, amide and imide.
A catalyst system comprising a combination of one or more compounds (b), an alkylaluminum compound (c) and a halogen-containing compound (d) is used, and the catalyst component (b)-
The catalyst component containing at least (c) and (d) in (d) is heated to 100 ° C. or higher, and then contacted with the rest of the catalyst component and α-olefin. Then, it is preferable to bring the α-olefin into contact with the chromium-based catalyst in such a manner that the chromium compound (a) and the alkylaluminum compound (c) do not come into contact with each other in advance. According to such a specific contact mode, it is possible to selectively carry out the trimerization reaction and obtain 1-hexene from the raw material ethylene in a high yield.

The above-mentioned specific contact mode is specifically as follows.
(1) A method of introducing α-olefin and catalyst component (a) into a solution containing catalyst components (b) to (d), (2) α-in a solution containing catalyst components (c) and (d) Olefin,
A method of introducing the catalyst components (a) and (b), (3) a method of introducing α-olefin, the catalyst components (c) and (d) into a solution containing the catalyst components (a) and (b), (4)
It can be carried out by a method of introducing α-olefin and catalyst components (b) to (d) into a solution containing the catalyst component (a).

In each of the above methods, each solution is usually prepared by using a reaction solvent and contains at least (c) and (d) of the catalyst components (b) to (d). The ingredients are heated above 100 ° C. For example, in the case of the above-mentioned introduction method (1), α-olefin and the catalyst component (a) are introduced into a solution which is preheated to 100 ° C. or higher and contains the catalyst components (b) to (d). Also, 100 ℃
After the catalyst component (b) is introduced into the solution which has been heated in advance and contains the catalyst components (c) and (d), the α-olefin and the catalyst component (a) are introduced.

The preheating temperature of the catalyst component must be 100 ° C. or higher, but if the temperature is too high, the alkylaluminum compound (c) or the like may be metallized. To be done. A preferable temperature for preheating is 110 to 180 ° C, and a particularly preferable temperature is 120 to 160 ° C. Although the preheating time depends on the preheating temperature, it is usually 5 to 120 minutes,
It is preferably in the range of 30 to 90 minutes. The reason why the preheating in the present invention enhances the selectivity of the catalytic reaction is presumed to be due to the specific three-dimensional structure of the chromium-based catalyst obtained from the preheated catalyst component, but it is not always clear.

In the present invention, "a mode in which a chromium compound and an alkylaluminum compound do not come into contact in advance"
Means not only at the start of the reaction, but also after the additional α-
It means that such a mode is maintained in the supply of the olefin and the catalyst component to the reactor. However, the particular embodiment described above is the preferred embodiment required in the preparation of the catalyst and is irrelevant after the catalyst has been prepared, thus the catalyst recovered from the reaction system is It can be recycled without contradiction.

The reason why the activity of the low polymerization reaction of α-olefin becomes low when the chromium-based catalyst is used in such a manner that the chromium compound and the alkylaluminum compound are in contact with each other in advance is not clear yet, but it is presumed as follows. To be done.

That is, it is considered that when the chromium compound and the alkylaluminum are brought into contact with each other, the ligand exchange reaction proceeds between the ligand coordinated with the chromium compound and the alkyl group in the alkylaluminum compound. And, the alkyl-chromium compound produced by such a reaction is unstable in itself, unlike the alkyl-chromium compound obtained by a usual method. Therefore, alkyl-
The decomposition / reduction reaction of the chromium compound preferentially proceeds, and as a result, inappropriate demetallation is induced in the low polymerization reaction of α-olefin, and the activity of the low polymerization reaction of α-olefin decreases.

In the present invention, as the raw material α-olefin, a substituted or unsubstituted α-olefin having 2 to 30 carbon atoms is used. Specific examples include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene and the like. Particularly, ethylene is suitable as the raw material α-olefin, and 1-hexene, which is a trimer of ethylene, can be obtained from ethylene in high yield and high selectivity.

In the present invention, as a reaction solvent, butane, pentane, 3-methylpentane, hexane, heptane, 2-methylhexane, octane, cyclohexane,
C1-C20 chain or alicyclic saturated hydrocarbons such as methylcyclohexane, 2,2,4-trimethylpentane and decalin, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, mesitylene and tetralin Is used. These may be used alone or as a mixed solvent.

Further, as the reaction solvent, α-olefin as the reaction raw material itself or α-olefin other than the main raw material can be used. As the reaction solvent, α-olefin having 4 to 30 carbon atoms is used, and α-olefin which is liquid at room temperature is particularly preferable.

Particularly, the reaction solvent has 4 to 1 carbon atoms.
Chain saturated hydrocarbons or alicyclic saturated hydrocarbons of 0 are preferred. By using these solvents, it is possible to suppress the by-product of the polymer, and further, when the alicyclic hydrocarbon is used, there is an advantage that a high catalytic activity can be obtained.

In the present invention, the amount of chromium compound used is usually 1.0 × 10 ^{−7 to} 0.
5 mol, preferably 1.0 × 10 ^{−6 to} 0.2 mol,
More preferably, it is in the range of 1.0 × 10 ^{−5 to} 0.05 mol. On the other hand, the amount of the alkylaluminum compound used is usually 50 mmol or more per 1 mol of the chromium compound, but it is preferably 0.1 mol or more from the viewpoint of catalytic activity and selectivity of the trimer. And the upper limit is usually 1.0 × 10 ⁴ mol. Also, amine,
The amount of each amide or imide used is 1 mol of the chromium compound.
The amount is usually 0.001 mol or more, preferably 0.005 to 1000 mol, and more preferably 0.01.
It is set in the range of ˜100 mol. The amount of halogen-containing compound used is in the same range as the amount of amine, amide or imide used.

In the present invention, the chromium compound (a),
The molar ratio (a) :( b) of at least one compound (b) selected from the group of amines, amides and imides, the alkylaluminum compound (c) and the halogen-containing compound (d):
(C) :( d) is 1: 0.1-10: 1 to 100: 0.
1-20 are preferable and 1: 1-5: 5-50: 1-10
Is particularly preferable. By combining under such specific conditions, for example, hexene can be produced as an α-olefin low polymer in a yield of 90% or more (ratio to the total amount produced), and the purity of 1-hexene in hexene is high. To 99%
It can be increased above.

The reaction temperature is usually 0 to 250 ° C, preferably 0 to 150 ° C, more preferably 20 to 100 ° C. On the other hand, the reaction pressure is from normal pressure to 250 kg / cm ²
However, it is usually 100 kg / cm ²
Is sufficient. The residence time is usually in the range of 1 minute to 20 hours, preferably 0.5 to 6 hours. Coexistence of hydrogen during the reaction is preferable because improvement of catalytic activity and selectivity of trimer can be observed. In addition, the coexistence of hydrogen has an effect that the property of the by-produced polymer becomes powdery with less adhesion. The amount of hydrogen to coexist is usually 0.1 to 100 kg / c as hydrogen partial pressure.
m ² , preferably in the range of 1.0 to 80 kg / cm ² .

Separation and removal of the by-produced polymer in the reaction solution is carried out by appropriately using a known solid-liquid separation device, and the recovered α
-Olefin low polymer is purified if necessary. Distillation purification is usually employed for purification, and the target component can be recovered in high purity. In the present invention, in particular, highly pure 1-hexene can be industrially advantageously produced from ethylene. Then, by a polymerization reaction using a known polymerization catalyst, 1-obtained by the production method of the present invention
L-LDPE, which is a useful resin, can be produced from hexene.

[0052]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.

Example 1 A 2 L autoclave that had been heated and dried in a drier at 120 ° C. was assembled while hot, and then vacuum nitrogen substitution was performed. The autoclave was equipped with a catalyst component feed tube equipped with a rupture plate. n-heptane (730 ml), 2,5-
A solution of dimethylpyrrole (0.140 mmol) in n-heptane, triethylaluminum (0.700 mmo
l) in n-heptane, 1,1,2,2-tetrachloroethane (39.4 mg, 0.235 mmol) in n-
Charge the heptane solution to the barrel side of the autoclave, while
A catalyst component feed tube was charged with a solution of chromium (III) 2-ethylhexanoate (22.5 mg, 0.047 mmol) in n-heptane. The total amount of n-heptane is 750.
It was ml.

First, 2,5-dimethylpyrrole, triethylaluminum and 1,1,2, in an autoclave
The mixture of 2-tetrachloroethane was heated to 120 ° C., kept for 1.0 hour, cooled to 80 ° C., and then ethylene was introduced through the catalyst component feed tube. The rupture plate ruptured due to ethylene pressure, and the chromium compound was introduced into the barrel side of the autoclave to start low polymerization of ethylene. Ethylene was introduced until the total pressure reached 35 Kg / cm ² G, after which the total pressure was maintained at 35 Kg / cm ² G and the temperature was maintained at 80 ° C.

After the reaction for 0.5 hour, the pressure in the autoclave was released to degas, and the by-produced polymer (mainly polyethylene) in the reaction solution was separated and removed by a filter to obtain an α-olefin low polymer. Recovered. Table 1 shows the results of the composition analysis of the α-olefin low polymer by gas chromatography.

Example 2 In Example 1, 2,5-dimethylpyrrole, triethylaluminum and 1,1,2,3 in the autoclave were used.
The heating temperature of the mixture of 2-tetrachloroethane is 140 ° C.
An α-olefin low polymer was produced in the same manner as in Example 1 except that the composition was analyzed, and the results of composition analysis are shown in Table 1.

Example 3 In Example 1, n-heptane (730 ml) and triethylaluminum (0.70) were added on the barrel side of the autoclave.
0 mmol) in n-heptane, 1,1,2,2-tetrachloroethane (39.4 mg, 0.235 mmo)
1) n-heptane solution was charged, and a catalyst component feed tube was charged with chromium (III) 2-ethylhexanoate (22.5 m).
g, 0.047 mmol) in n-heptane and 2,5
Example 1 except that a solution of -dimethylpyrrole (0.140 mmol) in n-heptane was charged and the mixture of triethylaluminum and 1,1,2,2-tetrachloroethane in the autoclave was heated to 120 ° C. An α-olefin low polymer was produced in the same manner, and the results of composition analysis and the like are shown in Table 2.

Comparative Example 1 In Example 1, 2,5-dimethylpyrrole, triethylaluminum and 1,1,2,2 in the autoclave were used.
An α-olefin low polymer was produced in the same manner as in Example 1 except that the mixture of 2-tetrachloroethane was not heat-treated, and the results of composition analysis and the like are shown in Table 2.

In Table 1, “HP” of solvent type is n-heptane, Cr (2EHA) ₃ of Cr compound type is chromium (III) 2-ethylhexanoate, TCE of halogen-containing compound type.
Represents 1,1,2,2-tetrachloroethane.

[0060]

[Table 1] ─────────────────────────────── Example 1 2 Pre-heat treatment: Temperature (° C) x time (Hr ) 120 × 1 140 × 1 Solvent type (amount: ml) HP (750) HP (750) Cr compound type Cr (2EHA) ₃ Cr (2EHA) ₃ Cr compound amount (mg) 22.5 22.5 Cr compound (mmol) (a ) 0.047 0.047 2,5-Dimethylprolol (mmol) (b) 0.140 0.140 Et ₃ Al (mmol) (c) 0.701 0.701 Halogen-containing compound type TCE TCE Halogen-containing compound (mmol) (d) 0.240 0.240 Catalyst component molar ratio ( a: b: c: d) 1: 3: 15: 5 1: 3: 15: 5 Reaction temperature (℃) 80 80 Ethylene pressure (Kg / cm ² G) 35 35 Reaction time (Hr) 0.5 0.5 <Product amount (g)> 159.6 137.9 <Composition distribution (wt%)> C ₄ 0.1 0.0 C ₆ overall 95.4 97.0 1-hexene content in C ₆ (wt%) 99.1 99.5 C ₈ 0.4 0.5 C _10-20 4.0 2.5 By-product PE 0.00 0.00 ────────────────────────────────

[0061]

[Table 2] ─────────────────────────────── Example Comparative Example 3 1 Pre-heat treatment: Temperature (° C) x time (Hr) 120 × 1 None Solvent type (amount: ml) HP (750) HP (750) Cr compound type Cr (2EHA) ₃ Cr (2EHA) ₃ Cr compound amount (mg) 22.5 22.5 Cr compound (mmol) (a ) 0.047 0.047 2,5-Dimethylprolol (mmol) (b) 0.140 0.140 Et ₃ Al (mmol) (c) 0.701 0.701 Halogen-containing compound type TCE TCE Halogen-containing compound (mmol) (d) 0.240 0.240 Catalyst component molar ratio ( a: b: c: d) 1: 3: 15: 5 1: 3: 15: 5 Reaction temperature (℃) 80 80 Ethylene pressure (Kg / cm ² G) 35 35 Reaction time (Hr) 0.5 0.5 <Product amount (g)> 141.6 150.0 <Composition distribution (wt%)> C ₄ 0.2 0.4 C ₆ overall 94.0 89.0 1-hexene content in C ₆ (wt%) 98.1 97.6 C ₈ 0.5 0.7 C _10-20 5.2 9.8 PE by-product 0.00 0.02 ────────────────────────────────

[0062]

According to the present invention described above, there is provided a method for producing an α-olefin low polymer using a specific chromium-based catalyst, and particularly, an α-olefin low polymer mainly composed of 1-hexene from ethylene. Provided is a method for producing an industrially advantageous α-olefin low polymer capable of producing a polymer in high yield and high selectivity.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location // C07B 61/00 300 C07B 61/00 300 (72) Inventor Shinji Iwade Shiodo, Kurashiki, Okayama Prefecture 3-10-10 Mitsubishi Chemical Co., Ltd. Mizushima R & D Laboratory (72) Inventor Miaki Namba 3-10 Shiodori, Kurashiki-shi, Okayama Mitsubishi Chemical Corporation Mizushima R & D Laboratory

Claims (4)

[Claims] 1. A method for producing an α-olefin low polymer using a chromium catalyst, wherein the chromium catalyst is at least one compound selected from the group consisting of a chromium compound (a), an amine, an amide and an imide. A catalyst system comprising a combination of (b), an alkylaluminum compound (c) and a halogen-containing compound (d) is used, and at least (c) and (d) of the catalyst components (b) to (d) are used in the reaction solvent. ) After heating the catalyst component containing
A method for producing an α-olefin low polymer, which comprises contacting the remaining catalyst component and α-olefin. 2. The α- according to claim 1, wherein the halogen-containing compound (d) is a halogen-containing compound containing an element selected from the group IIIA, IIIB, IVA, IVB, VA and VB of the periodic table. Method for producing olefin low polymer. 3. A molar ratio of catalyst components (a) :( b):
(C): (d) is 1: 0.1-10: 1 to 100: 0.
It is 1-20, The manufacturing method of the alpha-olefin low polymer of Claim 1 or 2. 4. The α-olefin low polymer according to claim 1, wherein the α-olefin is brought into contact with the chromium-based catalyst in such a manner that the chromium compound (a) and the alkylaluminum compound (c) are not brought into contact with each other in advance. Production method.